Process for the preparation of hydrogen by autocombustion.



G. F. JAUBERT. v PROCESS PoR THE PREPARATIUN or HYDROGEN BY AUTOGOMBUSTION.

AFPLIGATION FILED JAN.5, 1911.

l Patented June 11, 1912.

2 SHEETS-SHEET 1.

I jf/7555.65 v

G. P. JAUBERT. A PROCESS PQR THE PREPARATION OF HYDROGEN BY AUIQC0MBUSTI01\T.l

l APPL-ITION FILED JAN.5, v1911. l f 1,029,964, Patented June11,'1912.

Figa 'Geenen FRANoIs'JAUgBEnr, orA Penis, FRANCE.

To all whom it may concern: y

Be itknown that I, GEORGE, FRANQOIS JAUBERT, of 155 Boulevard Malesherbes, Paris, France, have invented certain new and useful Improvements inl and Relating to Processes for the Preparation of Hydro-f gen by Autocombustion, of-Wliich the following is a specification.`V

-This invention relates to an improved .method of and apparatus for the preparaA tion of hydrogen by a auto-combustion.

A process for the preparation of hydrogen by a Wet operation is known which condry process and by sists in causing a metal (aluminium, zinc or l alloys or combinations of these metals) or a metalloid (silicon) to re-actupon an alka-l lline solution (caustic soda or potash lye,

milk of linie, etc). If, on the other hand these same met-als or4 this metalloid are 'mixed in the pulverulent and dry state such for example as aluminium, zinc or their alloys, silicon or its combinations vwith the alkaline or alkaline-earth liydrates such as caustic potash or soda hydrated lime, etc., likewise in powder and in the dry state, n0 re-action arises. I ha e discovered vthat certain of these mixtures (of metals or metalH loids and alkaline hydrates) Wliicli.are abf solutely stable when cold decompose of themselves if their mass has been kindled at a spot and that this decomposition takes place with a violent liberation of hydrogen.

The process in accordance with the in- I vciition consists in producing the action in a pulverulent anddry state and at a high vtemperature Without the intervention of external heating (kindling the mass at a point) of metals or their alloys such as aluminium, zinc or metalloidsor their combinations such as silicon, carbonor mixtures thereof upon alkaline or alkaline-earth hy drates, likewise in the pulvcrulent and dry state.

The process is most particularly appli! f cable when the bodies in `contact combine -one with the otheifdirectly, that is to say,

affinity or but little atlinity for each other fand do not combine voluntarily merely asa result of kindling them ata point. In this case the process is somewhat modified in order to render the above process by a dryi t specification of Letters Patent. l Patented June 1,1, Application led January 5, 1911. Serial No. 600,859. i

PROCESS THE PREPARATION IHYLDRGEN BY AUTOCOMBUSTION.

method, applicable .to a Whole series o/f metals, metalloids oii alloys, owing to the inter-` ventionof an oxidizing agent or c'iniburent. This-modified form of the process essentially consists in kindling in a closed vesselA av mixture composed vof an excess of combustible (metal,.1netalloi,d or alloy) and of a comburent or oxidizing agent capable of supporting combustion in Iche said closed vessel in the presence of Waiter vapor. This Water vapor may arise in the mixture itself in-Whicliliydiates have' been incorporated; V

that is to say, any aqueous body or body containing hydrogen and oxygen capable of decoinposing under heat in liberating Water vapor as for example slaked glime, alcohoh ates, carbohydrates and even Water which is nothing other than a perfect hydrate. This Water vapor might likewise be supplied Wholly or partially from the exterior and be produced Wholly orpartially at the 'exterior by any appropriate means and more particularly in utilizing the heat of combustion. of the mixtures referred to above for vaporizing the. Water of a boiler as would bedone with anordinary 'fuel In order to ,facilitate the explanations which follow, embodiments of apparatus forcarrying the process into practice have been represented in the accompanying drawing: Figure 1 is acsectional vievv of an apparatus for obtaining compressed hydrogen; l Fig. 2 is an apparatus for obtaining hydrogen under a small pressure; Fig. 3 is a detail vieiv; Figs. l and A5 are respectively a side elevationand an end viewpof a portable apparatus. y i

The apparatus according to Fig. l consists of a tube A-Al preferably a`w'eldless Y tube closed at one of its ends by ascrew plugv 'B and provided at its other end with a perforated bottom. C. This tube which forms 'the generator is supported. in a. casi-ng D which constitutes the gas reservoir D1. The

perforated bottom C forms in thisreservoirv va chamber F servingas purifier and conis .preparedin ,the pulyerulent and dry state priming yand kindling plug G is opened and .Hthrough the orifice thus formed a. ball of 'iron a match or other suitable material heated to a temperature which may vary between 400 and 500O C. is dropped. The

plug is then replaced and screwed home.

The reaction starts automatically and ex.

tends to the entire mass with great liberaltioii ott heat. The hydrogen is liberated, ac cumulates under pressure in the reservoir l)1 2o from which it can be taken as required.

The following may be given as examples of mixtures furnishing goed results:

lierro-silieon at 90 to. 95% ot silicon i in an inipalpable powder 2. 500 Hydrated lime in powder Q. 000 Caustic soda in powder (i. 000

These various ingredients atter-being intimately niixed give a gray powder resenr bling cement, stable when cold and gradually attracting the humidity orn the air.

After kindling tlie'reaction is so vigorous that the entire mass is caused to become incandescent; in certain cases an inert material can be added t'or moderatiner its vion n lcnce in accordance with Example Il below:

Eamplc II.

The chemical reactions that arise can be represented by the following equations:

lith aluminium Alg-l-(SNaOI-I: M2O4Na2+2Na2O+3HT Or in the presence of lime:

Or in the presence of lime:

sientan-Hostile);

siogiiaoaownz:

With carboni:

Cl-4NaOH=CO3Na. ,+Na2O-i-2H2.

Or in the presence of lime:

In order to obtain the maximum yield of hydrogen, hydrogen containingsubstanees can be added to the mixture such as the hydrates or bodies containing water of crystallization. crystallized carbonate of soda sulfate of soda sulfate of lime and so Jforth. It will ot course be understood that in the foregoing examples the silicon can be replaced by an equivalent quantity of aluminium or zinc or one of their alloys or of carbon or a mixture of these various simple bodies. Similarly the soda can be replaced by potash or lime or a mixture of these hydrates. The'mixtures mentioned can be formed into agglomerates in such a manner as toI constitute a commercial product of greater density and more easily handled and sold either in the 'torni ot briquets or inclosed in cartridges ready .tor introduction into the gas generator.

When the constituent elements ot the mixture have no or but little aflinity tor each other, the two following cases may be considered.

First caso.

lVhere the water vapor is incorporated directly in the mixture in one ot the forms mentioned above the process is carried into practice bypreparing a mixture possessing the three following properties:

y (l) Ot being combustible in a vessel.

(2) Of containing aqueous bodies, that is to say, bodies capable ot liberating water vapor (metallic liydrates, compounds containing water of hydration, ot' constitution. of interposition, carbo-hydrates, etc),

(3) Of containing a. metal or,metalloid one of their derivatives or a mixture ot the said bodies introduced in excess and capable of decomposing the water vapor at high temperature in liberating gaseous hydrogen.

In order to comply with the first ot these conditions theselected suliistance suchy tor` example as iron iny the form ot powder, powdered carbon and so forth is mixed with a comburent or an oxidizing agent (such as an oxygenated salt clilorate, or perchlorate ot' potasli or a metallic oxid, oxid of lead. manganese iron) or any other body capable of liberating oxygenl and supporting combustion in such a manner as to obtain a mixture in the form of powder stable in a cold closed Aie' state but combustible in a closed vessel inl liberating heat.

.With iron and chlorate of potash a tion of the following type is obtained.

In order to comply with the second of the conditions set forth there should be added to the above caloriiic mixture a substance capable of liberating water (such as a metallic rea@- hydrate in the form of powder like slaked lime CatOHQ for example or a compound containing water of crystallization (such as plaster CaSOrt-Qaq. bauxite Al2O+-H20, etc.)

or an alcoholate or a carbohydrate. Finally in order to meet the third condition there is added to the calorific mixture either an excess of combustible (iron, carbon, silicometc.) or one of their derivatives, ferro-silicon. ferrochroniium. ferro-borium. ferro-carbon. carbid of silicon, carbid of borium, carbid of calcium, aluminium, manganese or a hydrid such as hydrid of calcium Caldi2 hydi'id of chromium, etc., which excess of combustible .will in a hot state decompose the water vapor and permit of the liberation of hydrogen.

If carbon or a 'derivative containing carbon is employed there is a risk of the hydrogen being co-ntaminated by carbonic acid gas. This latter can `be eliminated either by adding to the mass an excess of alkaline hydrate which will retain the carbonic acid gas or by washing the impure hydrogen after it has been prepared in an alkaline lye. Good results are likewise obtained by replacing the metallic hydrates by metallic alcoholates or polylalcoliolates corresponding to the formula:

aoJrMe,

Similar equations are arrived at with silicon, carbon and other metals or metalloids.

The following can be given as examples of mixtures furnishing good results:

Eample I.

20 kgs. of iron powder. 10 of slaked lime.

6 of perchlorate of potash.

gray powder is obtained whicrhwhen kindled at a point burns rapidly in giving rise to Va violent liberation of hydrogen.l

Example II.

of ferro-Saadi with 75%. 0f Silicon.

2() kgs.

i of litharge.

60 of sodaliine (rds soda and -ird lime).

Example III.. 2 kgs. of .ferro-silicon with 75% of silicon.

0 5 of iron powder.

3 vof wlieaten tiour.

5 of lime.

3 of vchlorate of potash.

The 'auto-combustion of these conipositions or powders may take place in metal cartridges which at the same time serve for transporting and packing thein and which.

can be introduced into a suitable generating apparatus at tlieinoment of kindling.

Second Crm?.

prises a generator a surrounded by a water jacket Z), c and closed by a massive cover d' provided with a central hole closed by an obturator e. A vapor liberating pipe f provided with a cock 71. places the interior g of the generator in communication with the water jacket b, c forming a boiler. it its lower'part ya pipe 'i passes through the generator; this pipe presents a downwardly dirested. aperture j and is provided with a three-way cock lo; this cock opens into 'a liberating chimney m and into a pipe In which opens into a gas reservoir 0 divided by a cylinder p into two compartments q, 1

serving as purifying and drying chambers respectively. The purifying chamber qcon- -tains a certain quantity of water s and at its serves to liberate the hydrogen is contained (Fig.v 3) comprising"` in metal cartridges l a metal Aframe 2 which facilitates handling izo them; for the same reason the cover Z is 'providedwith handles 3 ending in rings. i The operation is as follows: The ca rtridges l charged with the mixtures reterred to above in the examples described under the first case, but from which the substances capable of liberating water may be partially or wholly omitted are introduced into the generator a where they rest upon the pipe i; the upper end is removed and the cover d fitted but not bolted so as to avoid the risk of an cxi'ilosion resulting from e.\:- cess pressure in the generator. The cover should be of sutiicieut weight to normally remain applied to the generator. The pipe is closed by means of the three-way cock a the mixture contained in they cartridge is then kindled t'or example by allowing a fusee to fall through the central hole e in the cover which is at once blocked. The combustion becomes propagated in thisl closed vessel, the water contained in c becomes heated vaporizes, and when the pressure gage 4 indicate a sutiicient pressure, approximatelyv 30 lbs. per square inch, the cock i is opened; The vapor enters the space g; encounters the mixture in process of combustion and the liberation of hydrogen commences. As already indicated at the moment of kindling the pipe hasI been placed in communication through the cock Vwith the liberation chimney m and this condition is maintained until a bluish smoke is seen to escape at m which indicates that all the air has been scavenged from the apparatus. The cock r is then turned in such a manner as to establish coimminication bef tween the generator (y1y and the reservoir 0 through the pipes i' and a.. The hydrogen is washed and purified in the purifier s, 1f, dried in i' and then conducted through the gas supply pipe 'a to the utilization appliances.

In order to obtain a continuous process a number of' generators might be grouped around the purifying reservoir 01,' in Fig. 2 two generators are shown.

The apparatus represented in Figs. 3 and 4 is more particularly intended for infiating war balloons in the field. The suitable number of `generators (1.', e2, a3. similar to those in Fig. 2 are arranged upon a carriage 5; they communicate through the pipe,y n, n, n3. y. with a scrubber 6 which cominunicates through a pipe 7 with a purifying reservoir 8. These figures show atl m', m2.I m3. the liberation chimneys and at c, 7a2, 7e3. the three-way cocks.

The inventionthus presents the advantage of permitting of marketing stable products which will keep and which are capable of liberating without manipulation and in very simple apparatus pure hydrogen under pressure. Instead of an iron ball a percussion tube or any other method of kindling can be utilized.

The invention is applicable to all cases where a rapid liberation of hydrogen is required and more particularly for arostation.

lhat I claim is l. The herein described process for the preparation of hydrogen by auto-combustion, which consists in causing metals of the kind described to act at a high teniperature without external heating upon alkaline hydrates of the kind described.

Q` The herein described process for the preparation of hydrogen by auto-combustion, which consists in causing dry-and pul.

verulent metals of the kind described to act at a high temperature without external heating upon dry and pulverulent alkaline hydrates ot' the kind described.

3. The herein described process 4for the preparation of hydrogen by auto-combustion, which, consists in forming a mixture, stable when cold, of metals of the kind described and alkaline hydrates ot' the kind described, and then kindling the mixture.

4. The herein described process for the preparation of hydrogen by auto-combustion, which consists in forming a dry pulverulent mixture, stable when cold. of metals of the kind described, and dr and pulverulent alkaline hydrates of the kind described, and then kindling the mixture.

n testimony whereof I have hereunto placed my. hand at Paris (France), this twenty-third day of December, 1910.

GEORGE FRANQOIS JAUBERT.

In the presence of two witnesses:

H. C. Coxn, HENRY SCHWAB. 

